Process for the manufacture of halocarbons

ABSTRACT

A liquid phase process is disclosed for producing halogenated alkane adducts of the formula: CAR 1  R 2  CBR 3  R 4  (where, A, B, R 1 , R 2 , R 3  and R 4  are defined in the specification) which involves contacting a corresponding halogenated alkane, AB, with a corresponding olefin, CR 1  R 2  ═CR 3  R 4 , in the presence of a catalyst system containing (i) at least one catalyst selected from monovalent and divalent copper, and (ii) a promoter selected from aromatic or aliphatic hetercyclic compounds which contain at least one carbon-nitrogen double bond in the heterocyclic ring. When hydrochlorofluorocarbons are formed, hydrofluorocarbons may be formed therefrom by reacting the hydrochlorofluorocarbons with HF.

This application is a national filing under 35 USC 371 of InternationalApplication No. PCT/US96/12548 filed Jul. 31, 1996, which claimspriority of U.S. Provisional Application No. 60/001,702 filed Aug. 1,1995.

FIELD OF THE INVENTION

This invention relates to a process for the manufacture of halogenatedalkanes by the catalytic reaction of haloalkanes with halogenatedolefins.

BACKGROUND

The catalyzed radical addition of haloalkanes to olefins is a well knownreaction. Typically, however, when a haloalkane (e.g., AB, where A is asubstituted carbon atom and B is a halogen other than fluorine) is addedto an olefin (e.g., CH₂ ═CHR) to form the saturated adduct (e.g., CH₂ACHBR), the products (i.e., halogenated addition compounds) also includevarying amounts of telomers (e.g., A(CH₂ CHR)_(n) B, where n is equal to2 or more). For example, Canadian Pat. No. 2,073,533 discloses a processfor the manufacture of CCl₃ CH₂ CCl₃ by reacting carbon tetrachloridewith vinylidene chloride using copper catalysts in acetonitrile. Theselectivity for CCl₃ CH₂ CCl₃ with respect to converted vinylidenechloride was 87%. It has been shown in the art that the major by-productis the C₅ telomer, CCl₃ (CH₂ CCl₂)₂ Cl.

The halogenated adducts are useful intermediates for the production offluoroalkanes, particularly, hydrofluoroalkanes. These latter compoundsare useful as refrigerants, fire extinguishants, heat transfer media,gaseous dielectrics, sterilant carriers, polymerization media,particulate removal fluids, carrier fluids, buffing abrasive agents,displacement drying agents, propellants, foaming agents and power cycleworking fluids. There is an interest in developing more efficientprocesses for the manufacture of hydrofluoroalkanes.

SUMMARY OF THE INVENTION

A liquid phase process is provided in accordance with this invention forproducing halogenated alkane adducts of the formula CAR¹ R² CBR³ R⁴wherein R¹, R², R³, and R⁴ are each independently selected from thegroup consisting of H, Br, Cl, F, C₁ -C₆ alkyl, CN, CO₂ CH₃, CH₂ Cl, andaryl (e.g., phenyl), provided that only two of R¹, R², R³, and R⁴ can beselected from C₁ -C₆ alkyl, CN, CO₂ CH₃, CH₂ Cl, and aryl; A is selectedfrom the group consisting of CX₃, CH_(3-a) X_(a), C_(n) H.sub.(2n+1)-bX_(b) and CH_(c) X_(2-c) R, where R is C_(n) H.sub.(2n+1)-b X_(b) (e.g.,CF₃ and CCl₂ CF₃), each X is independently selected from the groupconsisting of Br, Cl and I, a is an integer from 0 to 3, n is an integerfrom 1 to 6, b is an integer from 1 to 2n+1, and c is an integer from 0to 1; and B is selected from the group consisting of Br, Cl and I;provided that (1) when A is CX₃ then only one of X is I, (2) when A isCH_(3-a) X_(a), then each X is B and a is an integer from 1 to 2 when Bis Br, a is 2 when B is Cl, and a is an integer from 0 to 2 when B is I,and (3) when A is C_(n) H.sub.(2n+1)-b X_(b), then each X isindependently selected from Cl and F, and B is I. The process comprisescontacting a halogenated alkane of the formula AB (where A and B are asindicated above) with an olefin of the formula CR¹ R² ═CR³ R⁴ (where R¹,R², R³ and R⁴ are as indicated above) in the presence of a catalystsystem containing (i) at least one catalyst selected from the groupconsisting of monovalent and divalent copper, and (ii) at least onepromoter selected from the group consisting of aromatic or aliphaticheterocyclic compounds which contain at least one carbon-nitrogen doublebond in the heterocyclic ring.

This invention further provides a process for producinghydrofluoroalkanes (e.g., CF₃ CH₂ CHF₂). This process comprises (a)producing a hydrochlorofluoroalkane (e.g., CCl₃ CH₂ CHCl₂) by reacting ahalogenated alkane of the formula AB (e.g., CCl₄) and an olefin of theformula CR¹ R² ═CR³ R⁴ (e.g., CH₂ ═CHCl) as indicated above (providedthat B and X are Cl and at least one of said reactants containshydrogen), and (b) reacting the hydrochlorofluoroalkane produced in (a)with HF.

DETAILED DESCRIPTION

The present invention provides a liquid phase process for themanufacture of halogenated alkanes of the formula CAR¹ R² CBR³ R⁴ bycontacting a corresponding halogenated alkane, AB, with a correspondingolefin, CR¹ R² ═CR³ R⁴, in the presence of a copper catalyst (Cu⁺ and/orCu⁺⁺) and a promoter (containing a C═N ring bond).

Examples of halogenated alkanes of the formula AB, where A and B are asdefined above, include, CBrCl₃, CBrF₃, CCl₄, CCl₃ F, CCl₂ F₂, CF₃ I,CCl₂ FCCl₂ F, CCl₃ CF₃, CCl₃ (CF₂ CF₂)_(q) Cl (where q is an integerfrom 1 to 6), CCl₃ CH₂ CF₃, CCl₃ CF₂ CF₃, CCl₃ CH₂ CCl₃, CF₃ CF₂ I andCF₃ CF₂ CF₂ I.

Examples of olefins of the formula CR¹ R² ═CR³ R⁴, where R¹, R², R³ andR⁴ are as defined above, include, CF₂ ═CF₂, CF₂ ═CClF, CF₂ ═CCl₂,CClF═CClF, CClF═CCl₂, CF₂ ═CHF, CF₂ ═CH₂, CHF═CHF, CHF═CH₂, CH₂ ═CH₂,CH₂ ═CHCH₃, CH₂ ═CHCF₃, CH₂ ═CFCF₃, CH₂ ═CHCl, CH₂ ═CCl₂, CHCl═CHCl,CHCl═CCl₂, CH₂ ═CHCl, CH₂ ═CHCH₂ Cl, CH₂ ═CHAryl (e.g., CH₂ ═CHC₆ H₅),CH₂ ═CHCO₂ CH₃, CH₂ ═C(CH₃)CO₂ CH₃, CH₂ ═CHCO₂ C₂ H₅, and CH₂ ═C(CH₃)CO₂ C₂ H₅.

The addition of halogenated alkanes to alkenes (i.e., olefins) to formthe corresponding adducts is catalyzed by copper compounds in the +1 or+2 oxidation state. Preferred copper compounds for the process of thisinvention include copper(I) chloride, copper(II) chloride, copper(I)bromide, copper(II) bromide, copper(I) iodide, copper(II)acetate andcopper(II) sulfate. The catalysts are preferably anhydrous; andpreferably, the addition is done under substantially anhydrousconditions in the substantial absence of oxygen. Without wishing to bebound by theory, it is believed that the effect of the catalyst is toenhance the yield of the 1:1 addition product (i.e., the adduct) of thehalogenated alkanes to the alkene relative to higher molecular weighttelomers that are known in the art.

Suitable promoters for use in the catalyst system include those selectedfrom the group consisting of imidazoles, imidazolines, oxadiazoles,oxazoles, oxazolines, isoxazoles, thiazoles, thiazolines, pyrrolines,pyridines, trihydropyrimidines, pyrazoles, triazoles, triazolium salts,isothiazoles, tetrazoles, tetrazolium salts, thiadiazoles, pyridazines,pyrazines, oxazines and dihydrooxazine. Preferred promoters includethose selected from the group having Formula (I) or Formula (II) asfollows: ##STR1## wherein E is selected from the group consisting of--O--, --S--, --Se--, --CH₂ --, and --N(R⁸)--; R⁵ is selected from thegroup consisting of CH₃ and C₂ H₅ (and is preferably CH₃); R⁶ and R⁷ areselected from the group consisting of H, CH₃, C₆ H₅ (i.e., phenyl), CH₂C₆ H₅, CH(CH₃)₂, and fused phenyl; L is selected from the groupconsisting of --O--, --S--, --Se--, --NR⁸ --, --C₆ H₄ --, 2,6-pyridyl,--OC₆ H₄ --C₆ H₄ O--, --CH₂ CH₂ OCH₂ CH₂ --, and --(CH₂)_(p) -- where pis an integer from 0 to 6; and each R⁸ is selected from the groupconsisting of H and C_(m) H_(2m+1) where m is an integer from 1 to 6.The bond between each pair of carbon atoms respectively attached to R⁶and R⁷ (as represented by the dashed bond lines in Formula (I) andFormula (II)) can be either a single or a double bond. Of note arecompounds of Formula (II) which are optically active.

The reaction is done in the liquid phase, normally in the presence ofsolvents such as acetonitrile, dimethyl sulfoxide, dimethyl formamide,tetrahydrofuran, isopropanol, t-butanol, polyethers of the formula R⁹O(CH₂ CH₂ O)_(r) R⁹ where each R⁹ is independently selected from thegroup consisting of H, CH₃ and C₂ H₅ and r is an integer from 1 to 4,esters of formula R¹⁰ CO₂ R¹⁰ where each R¹⁰ is independently selectedfrom C₁ -C₆ alkyl groups and mixtures thereof; acetonitrile beingpreferred. Also of note are systems wherein the solvent divides thereaction mixture into two liquid phases. Reference is made to U.S.Patent Application No. 60/001,702 one of the priority documents for PCTInternational Publication No. WO 97/05089, which is hereby incorporatedby reference, for further disclosure relating to such solvent systems.

The catalyst system comprising the copper compound and promoter asdisclosed above can be prepared in the solvent in advance in a suitablemixing vessel, and then added to the reaction mixture. Alternatively,the individual components of the catalyst system can be addedindividually to the reactor. Of note are embodiments where the reactionis accomplished in a homogeneous system (i.e., where the catalyst isdissolved).

Telomer formation can be somewhat controlled by manipulating reactionvariables such as the molar ratio of halogenated alkane, AB, to olefin,CR¹ R² ═CR³ R⁴ or by adding the olefin to the halogenated alkane. Highermolar ratios of AB:CR¹ R² ═CR³ R⁴ and dilution of the olefin reducetelomer formation. However, for the addition of CCl₄ to CH₂ ═CCl₂ thehighest ratio of the C₃ adduct CCl₃ CH₂ CCl₃ to the C₅ adduct wasreported to be 9:1 (see Belbachir et al., Makromol. Chem.1984, 185,1583-1595).

The amount of catalyst used in the reaction of this invention istypically at least about 5 mmol, and preferably from about 10 mmol to100 mmol, per mole of olefin, CR¹ R² ═CR³ R⁴, used.

The amount of halogenated alkane starting material used in the reactionof this invention is typically at least about 1 mmol, and preferablyfrom about 2 mmol to 10 mmol, per mmol of alkene used.

The amount of promoter used in the reaction of this invention istypically at least an amount sufficient to provide 2 mmol ofheterocyclic ring which contains carbon-nitrogen double bonding per mmolof copper catalyst. For example, typically at least about 2 mmol ofFormula (I) promoter or at least about 1 mmol of Formula (II) promoter,and preferably from about 4 mmol to 10 mmol of Formula (I) promoter orfrom about 2 mmol to 5 mmol of Formula (II) promoter is used per mmol ofcopper catalyst used.

The process of the present invention is suitably conducted at atemperature in the range of from about 50° C. to 150° C., preferablyfrom about 80° C. to about 130° C.

The pressure of the process is not critical and can be subatmospheric,atmospheric or superatmospheric, preferably, superatmospheric. Thereaction products may be separated by conventional techniques such asdistillation.

Of note is the embodiment where AB is CCl₄ and CR¹ R² ═CR³ R⁴ is CH₂═CCl₂. The isolated 1,1,1,3,3,3-hexachloropropane adduct can then bereacted with hydrogen fluoride to produce CF₃ CH₂ CF₃ (e.g., asdisclosed in U.S. Pat. No. 5,414,165).

The reaction zone and its associated feed lines, effluent lines andassociated units should be constructed of materials resistant tocorrosion. Typical materials of construction include steel reactorslined with poly(tetrafluoroethylene) or glass and glass reactors.

The addition compounds that comprise the products of this invention areuseful as intermediates for the formation of hydrofluoroalkanes. Theseaddition compounds can be reacted with hydrogen fluoride in either theliquid or vapor phase in the presence of a suitable fluorinationcatalyst.

In the liquid phase, the addition compounds can be reacted with HF inthe presence of catalysts selected from the halides of antimony,molybdenum, niobium, tantalum, tin and titanium, and mixtures thereof,preferably, antimony, niobium and tantalum. The temperature of thereaction can be in the range of 50° C. to 175° C., preferably, 60° C. to150° C. The pressure is selected so that the reaction medium ismaintained in the liquid state, typically between 101 kPa and 5000 kPa,preferably, 1135 kPa to 3203 kPa. For example,1,1,1,3,3,3-hexachloropropane (HCC-230fa) can be reacted with HF in theliquid phase using halides, fluorosulfonates or triflates of antimony,molybdenum, niobium, tantalum, tin or titanium, or mixtures thereof ascatalysts to produce 1,1,1,3,3,3-hexafluoropropane (HFC-236fa).1-Chloro-1,1,3,3,3-pentafluoropropane (HCFC-235fa) can also be preparedfrom HCC-230fa. HCFC-235fa can be hydrodechlorinated using ahydrodehalogenation catalyst to produce 1,1,1,3,3-pentafluoropropane(HFC-245fa). Palladium on acid-washed carbon is a preferred catalyst forthe coversion of HCFC-235fa to HFC-245fa.

In another embodiment of this invention carbon tetrachloride can bereacted with vinyl chloride to produce the adduct1,1,1,3,3-pentachloropropane (i.e., CCl₃ CH₂ CHCl₂ or HCC-240fa). CCl₃CH₂ CHCl₂ can then be reacted with HF in the liquid phase using theprocess described above to produce CF₃ CH₂ CHF₂. The reaction productsmay be separated by conventional techniques such as distillation.Hydrofluorocarbons such as CF₃ CH₂ CHF₂ likely form azeotropes with HF;and conventional decantation/distillation may be employed if furtherpurification of the hydrofluorocarbons is desired.

In the vapor phase, the addition compounds can be reacted with HF in thepresence of catalysts comprising trivalent chomium. Catalysts preparedby pyrolysis of (NH₄)₂ Cr₂ O₇ to produce Cr₂ O₃ and pretreated with HFand catalysts prepared by pretreating Cr₂ O₃ having a surface areagreater than about 200 m² /g with HF are preferred. The temperature ofthe reaction can be in the range of 200° C. to 400° C., preferably, 250°C. to 375° C. The pressure is not critical and is selected so that thereaction starting materials and products are maintained in the vaporstate at the operating temperature. For example, it has recently beendisclosed in U.S. Pat. No. 5,414,165 that 1,1,1,3,3,3-hexafluoropropanemay be prepared in high yield from 1,1,1,3,3,3-hexachloropropane by avapor phase hydrofluorination process in the presence of a trivalentchromium catalyst.

Although the 1:1 addition compounds of the halogenated alkanes to thealkenes are the preferred products, the 2:1 adducts may also be usefulintermediates.

Without further elaboration, it is believed that one skilled in the artcan, using the description herein, utilize the present invention to itsfullest extent. The following preferred specific embodiments are,therefore, to be construed as merely illustrative, and does notconstrain the remainder of the disclosure in any way whatsoever.

EXAMPLE 1 CCl₄ +CH₂ ═CCl₂ →CCl₃ CH₂ CCl₃

A suspension of 10 mg (0.1 mmol) CuCl in 4 mL of MeCN was treated with 2equivalents of the promoter (i.e., ligand), except where notedotherwise, 114 mg of n-octane internal standard and 100 mg (1 mmol) ofCH₂ ═CCl₂. To this mixture was added 1.54 g (10 mmol) CCl₄. The glassreaction vessel was then pressurized with 200 psi (1480 kPa) N₂ andheated at 100° C. for 2 hr. The reaction mixture was analyzed by GC;results are summarized in Table 1, where % conversion is the molar %conversion of vinylidene chloride (i.e., CH₂ ═CCl₂), C₃ :C₅ is the molarratio of CCl₃ CH₂ CCl₃ to CCl₃ CH₂ CCl₂ CH₂ CCl₃, and the ligands usedare shown in the Legend; monodentate ligands are numbered 1-12 andbidentates are labeled with letters A-F. ##STR2##

                  TABLE 1                                                         ______________________________________                                        Run No.   Ligand       % Conv.  C.sub.3 :C.sub.5                              ______________________________________                                         1        A            100      24                                             2        B            97       41                                             3        C            100      76                                             4         1.sup.a     100      19                                             5        1            100      32                                             6         1.sup.b     100      49                                             7         1.sup.c     100      66                                             8.sup.d  1            100      49                                             9        11           100      >80                                           10        4            60       >80                                           11        8            80       >80                                           12        7            70       66                                            13        2            70       66                                            14        3            <50      49                                            15        5            >90      49                                            16        9            50       49                                            17        6            10       49                                            18        D            >90      13                                            19        E            20       49                                            20        12           >80      99                                            ______________________________________                                         .sup.a One equivalent of the promoter was used.                               .sup.b Four equivalents of the promoter was used.                             .sup.c Ten equivalents of the promoter was used.                              .sup.d The catalyst was CuCl.sub.2.                                      

Comparative Example No Promoter Added

The reaction was run in the same manner as that described in Example 1with the following differences; the catalyst used was CuCl₂ (0.1 mmol)and no promoter was used.

After 2 hours at 100° C., no conversion of CH₂ ═CCl₂ was observed.

EXAMPLE 2

Reaction of CuCl and Ligand F

To a solution of 215 mg (0.67 mmol) bbbo (Legend, structure F) in 5 mLof MeCN was added 65 mg (0.66 mmol) of CuCl to give a strawberry redsolution. The solution was filtered and 12 mL of Et₂ O were added. After20 hours, the resulting dark red crystals were filtered off, washed withEt₂ O and dried to give 110 mg [Cu(bbbo)₂ ][CuCl₂ ]. A second cropbrought the total yield to 210 mg (75%). The structure was confirmed byX-ray crystallography.

NMR Monitoring of Cu-catalyzed Addition of CCl₄ to Alkenes

In one series of experiments, the effect of added ligand2-Et-2-oxazoline was investigated using trans-β-Me-styrene as the alkenesubstrate. After 19 hr at 80° C., CuCl gave 14% conversion toPhCH(CCl₃)--CHClCH₃ with a diastereomeric ratio (DR) of 20. With 1 equivof ligand/Cu, conversion was 91% and the DR was 10. With 2 and 4 equiv,conversions were 96 and 100% with DRs of 9 and 7, respectively. Undersimilar reaction conditions, use of [Cu(bbbo)₂ ][CuCl₂ ] as catalystgave 92% conversion with a DR of 4.5. In another experiment with 4 equivof 2-Et-2-oxazoline/Cu, conversion was 30% after only 30 min. at 80° C.

Using trans-PhCH₂ CH═CHCH₃ as the alkene substrate, a comparison of2-Et-2-oxazoline, ethanolamine, and diethylamine ligands showed thatafter 1.5 hr conversions were 18, 3 and 1%, respectively.

EXAMPLE 3

Catalyst Selectivity and Lifetime Determination

These runs were done with only 0.5 mol % CuCl and a CCl₄ /CH₂ ═CCl₂ratio of one in order to differentiate promoters with respect toselectivity and lifetime. Reaction conditions: 4 mmol CCl₄, 4 mmol CH₂═CCl₂, 1 mL CD₃ CN, 0.02 mmol CuCl and 0.08 mmol promoter (0.04 mmol forbidentate promoters). Reactions were heated in NMR tubes at 85° C.Results are shown in the following table.

    ______________________________________                                        Run No.                                                                              Promoter time (hr)                                                                              % conv                                                                              % C.sub.3.sup.a                                                                     % C.sub.5 b                                                                         % C.sub.7.sup.c                    ______________________________________                                        1      1        9        40    79    18    3                                                  36       86    71    23    6                                                  70       100   72    23    5                                  2      2        9        47    84    16    --                                                 36       72    92    8     --                                                 70       100   88    12    --                                 3      10       9        4     67    23    --                                                 36       74    84    14    2                                                  70       100   85    13    2                                  4      F        9        22    94    6     --                                                 22       60    92    8     --                                                 70       100   94    6     --                                 5      C        9        20    84    14    2                                                  22       62    73    25    2                                                  70       100   77    20    3                                  6      none     72       97    80    18    2                                  ______________________________________                                         .sup.a C.sub.3 is CCl.sub.3 CH.sub.2 CCl.sub.3                                .sup.b C.sub.5 is CCl.sub.3 (CH.sub.2 CCl.sub.2).sub.2 Cl                     .sup.c C.sub.7 is CCl.sub.2 (CH.sub.2 CCl.sub.2).sub.3 Cl                

Runs 1 and 5 show decreasing selectivity with indicative of limitedpromoter lifetime. Run 4 sustained high selectivity for 200 turnovers.

EXAMPLE 4 CCl₄ +CH₂ ═CCl₂ →CCl₃ CH₂ CCl₃

CuCl (0.1 g), 2-ethyl-2-oxazoline (0.4 g), deoxygenated CH₃ CN (2 g),deoxygenated CCl₄ (16 g, 0.1 mol) and CH₂ ═CCl₂ (3 g, 0.031 mol) werecharged into a 100 mL Pyrex® flask equipped with a Teflon® value insidea dry box. The reaction mixture was kept 80° C. After 4 hours it wasanalyzed by GC. The conversion of CH₂ ═CCl₂ was 100%, the yield of CCl₃CH₂ CCl₃ was 92%, the selectivity of the reaction, defined as the ratioof CCl₃ CH₂ CCl₃ to CCl₃ CH₂ CCl₂ CH₂ CCl₃ was 97:3.

EXAMPLE 5 CCl₄ +CH₂ ═CF₂ →CCl₃ CH₂ CF₂ Cl

A mixture of CCl₄ (52 g, 0.33 mol) CH₃ CN (130 mL), CuCl (0.1 g) and2-ethyl-2-oxazoline (0.4 g), prepared inside a dry box, was loaded intoa 400 mL Hastelloy™ C nickel alloy shaker tube under N₂. The shaker tubewas closed, cooled to -78° C., evacuated and CH₂ ═CF₂ (6.5 g, 0.1 mol)was added. The reaction mixture was kept at 130° C. for 12 hours. Theshaker tube was then unloaded; the reaction mixture was washed withwater twice to remove CH₃ CN, dried over P₂ O₅ and the crude reactionmixture (40 g) analyzed by GC and ¹ H and ¹⁹ F NMR. The yield of CCl₃CH₂ CF₂ Cl was 70%, the selectivity of the reaction based on convertedolefin was 81%.

EXAMPLE 6 CCl₄ +CHF═CF₂ →C₃ HCl₄ F₃

Example 5 was repeated using the same amounts of reagents except thatCHF═CF₂ (8 g, 0.1 mol) was used instead of CH₂ ═CF₂. The isolatedproduct (41 g) contained, based on ¹ H, ¹⁹ F NMR and GC, CCl₄ (51%), C₃Cl₄ F₃ H (29%, two isomers in a 7:3 ratio), C₅ Cl₄ F₆ H₂ (8%, mixture ofisomers) and CH₃ CN (12%). The yield of isomeric propanes was 62%, theselectivity based on converted olefin was 60%.

EXAMPLE 7 CCl₄ +CHCl═CH₂ →CCl₃ CH₂ CHCl₂

Example 5 was repeated using the same amounts of reagents except thatCHCl═CH₂ (7 g, 0.1 mol) was used instead of CH₂ ═CF₂. The isolatedproduct (54 g) contained, based on ¹ H, ¹⁹ F NMR and GC, CH₃ CN, CCl₄,CCl₃ CH₂ CHCl₂ and a small amount of CCl₃ (CH₂ CHCl)_(n) Cl (n=2 and 3).The yield of CCl₃ CH₂ CHCl₂ was 69%, the selectivity based on convertedolefin was 64%.

EXAMPLE 8 CCl₄ +CH₃ CH═CH₂ →CCl₃ CH₂ CHClCH₃

Example 5 was repeated using the same amounts of reagents except thatpropylene (5 g, 0.1 mol) was used instead of CH₂ ═CF₂. The isolatedproduct (54 g) contained, based on ¹ H, ¹⁹ F NMR and GC, CH₃ CN, CCl₄,CCl₃ CH₂ CHClCH₃. The yield of CCl₃ CH₂ CHClCH₃ was 95%, the selectivitybased on converted olefin was >95%.

EXAMPLE 9 CCl₄ +CF₂ ═CF₂ →CCl₃ CF₂ CF₂ Cl

Example 5 was repeated using the same amounts of reagents except thattetrafluoroethylene (10 g, 0.1 mol) was used instead of CH₂ ═CF₂. Theisolated product (45 g) contained, based on ¹⁹ F NMR and GC, CCl₄(66.5%), CCl₃ CF₂ CF₂ Cl (23%), CCl₃ (CF₂ CF₂)₂ Cl (6%), CCl₃ (CF₂ CF₂)₃Cl (2.6%), CCl₃ (CF₂ CF₂)₄ Cl (1.4%), CCl₃ (CF₂ CF₂)₅ Cl (0.6%). Theyield of CCl₃ CF₂ CF₂ Cl was 40%, the selectivity based on convertedolefin was 65%.

EXAMPLE 10 CCl₃ CF₃ +CH₂ ═CH₂ →CF₃ CCl₂ CH₂ CH₂ Cl

Example 5 was repeated using the same amounts of reagents except thatethylene (4 g, 0.1 mol) and CCl₃ CF₃ (60 g, 0.3 mol) were used insteadof CH₂ ═CF₂ and CCl₄. The isolated product (45 g) contained, based on ¹⁹F NMR and GC, CCl₃ CF₃ (60%), CF₃ CCl₂ CH₂ CH₂ Cl (20%), CF₃ CCl₂ (CH₂CH₂)₂ Cl (10%), CF₃ CCl₂ (CH₂ CH₂)₃ Cl (2%) and CH₃ CN (8%). The yieldof CF₃ CCl₂ CH₂ CH₂ Cl was 70%, the selectivity based on convertedolefin was 63%.

What is claimed is:
 1. A liquid phase process for producing halogenatedalkane adducts of the formula CAR¹ R² CBR³ R⁴ whereinR¹, R², R³, and R⁴are each independently selected from the group consisting of H, Br, Cl,F, C₁ -C₆ alkyl, CN, CO₂ CH₃, CH₂ Cl, and aryl, provided that only twoof R¹, R², R³, and R⁴ can be selected from C₁ -C₆ alkyl, CN, CO₂ CH₃,CH₂ Cl, and aryl; A is selected from the group consisting of CX₃,CH_(3-a) X_(a), C_(n) H.sub.(2n+1)-b X_(b) and CH_(c) X_(2-c) R, where Ris C_(n) H.sub.(2n+1)-b X_(b), each X is independently selected from thegroup consisting of Br, Cl and I, a is an integer from 0 to 3, n is aninteger from 1 to 6, b is an integer from 1 to 2n+1, and c is an integerfrom 0 to 1; and B is selected from the group consisting of Br, Cl andI; provided that (1) when A is CX₃ then only one of X is I, (2) when Ais CH_(3-a) X_(a) then each X is B and a is an integer from 1 to 2 whenB is Br, a is 2 when B is Cl, and a is an integer from 0 to 2 when B isI, and (3) when A is C_(n) H.sub.(2n+1)-b X_(b) then each X isindependently selected from Cl and F and B is I, comprising: contactinga halogenated alkane of the formula AB with an olefin of the formula CR¹R² ═CR³ R⁴ in the presence of a catalyst system containing (i) at leastone catalyst selected from the group consisting of monovalent anddivalent copper, and (ii) at least one promoter selected from the groupconsisting of pyridazines, pyrazines, and aliphatic heterocycliccompounds which contain at least one carbon-nitrogen double bond in theheterocyclic ring.
 2. A liquid phase process for producing halogenatedalkane adducts of the formula CAR¹ R² CBR³ R⁴ whereinR¹, R², R³, and R⁴are each independently selected from the group consisting of H, Br, Cl,F, C₁ -C₆ alkyl, CN, CO₂ CH₃, CH₂ Cl, and aryl, provided that only twoof R¹, R², R³, and R⁴ can be selected from C₁ -C₆ alkyl, CN, CO₂ CH₃,CH₂ Cl, and aryl; A is selected from the group consisting of CX₃,CH_(3-a) X_(a), C_(n) H.sub.(2n+1)-b X_(b) and CH_(c) X_(2-c) R, where Ris C_(n) H.sub.(2n+1)-b X_(b), each X is independently selected from thegroup consisting of Br, Cl and I, a is an integer from 0 to 3, n is aninteger from 1 to 6, b is an integer from 1 to 2n+1, and c is an integerfrom 0 to 1; and B is selected from the group consisting of Br, Cl andI; provided that (1) when A is CX₃ then only one of X is I, (2) when Ais CH_(3-a) X_(a) then each X is B and a is an integer from 1 to 2 whenB is Br, a is 2 when B is Cl, and a is an integer from 0 to 2 when B isI, and (3) when A is C_(n) H.sub.(2n+1)-b X_(b) then each X isindependently selected from Cl and F and B is I, comprising:contacting ahalogenated alkane of the formula AB with an olefin of the formula CR¹R² ═CR³ R⁴ in the presence of a catalyst system containing (i) at leastone catalyst selected from the group consisting of monovalent anddivalent copper, and (ii) at least one promoter selected from the groupconsisting of imidazoles, imidazolines, oxadiazoles, oxazoles,oxazolines, isoxazoles, thiazoles, thiazolines, pyrrolines,trihydropyrimidines, pyrazoles, triazoles, triazolium salts,isothiazoles, tetrazoles, tetrazolium salts, thiadiazoles, pyridazines,pyrazines, oxazines and dihydrooxazine.
 3. A liquid phase process forproducing halogenated alkane adducts of the formula CAR¹ R² CBR³ R⁴whereinR¹, R², R³, and R⁴ are each independently selected from the groupconsisting of H, Br, Cl, F, C₁ -C₆ alkyl, CN, CO₂ CH₃, CH₂ Cl, and aryl,provided that only two of R¹, R², R³, and R⁴ can be selected from C₁ -C₆alkyl, CN, CO₂ CH₃, CH₂ Cl, and aryl; A is selected from the groupconsisting of CX₃, CH_(3-a) X_(a), C_(n) H.sub.(2n+1)-b X_(b) and CH_(c)X_(2-c) R, where R is C_(n) H.sub.(2n+1)-b X_(b), each X isindependently selected from the group consisting of Br, Cl and I, a isan integer from 0 to 3, n is an integer from 1 to 6, b is an integerfrom 1 to 2n+1, and c is an integer from 0 to 1; and B is selected fromthe group consisting of Br, Cl and I; provided that (1) when A is CX₃then only one of X is I, (2) when A is CH_(3-a) X_(a) then each X is Band a is an integer from 1 to 2 when B is Br, a is 2 when B is Cl, and ais an integer from 0 to 2 when B is I, and (3) when A is C_(n)H.sub.(2n+1)-b X_(b) then each X is independently selected from Cl and Fand B is I, comprising:.contacting a halogenated alkane of the formulaAB with an olefin of the formula CR¹ R² ═CR³ R⁴ in the presence of acatalyst system containing (i) at least one catalyst selected from thegroup consisting of monovalent and divalent copper, and (ii) at leastone promoter selected from the group having the Formula (I) or Formula(II) ##STR3## wherein E is selected from the group consisting of --O--,--S--, --Se--, --CH₂ --, and --N(R⁸)--; R⁵ is selected from the groupconsisting of CH₃ and C₂ H₅ ; R⁶ and R⁷ are selected from the groupconsisting of H, CH₃, C₆ H₅, CH₂ C₆ H₅, CH(CH₃)₂, and fused phenyl; L isselected from the group consisting of --O--, --S--, --Se--, --N(R⁸)--,--C₆ H₄ --, 2,6-pyridyl, --OC₆ H₄ --C₆ H₄ O--, --CH₂ CH₂ OCH₂ CH₂ --,and --(CH₂)_(p) -- where p is an integer from 0 to 6; and each R⁸ isselected from the group consisting of H and C_(m) H_(2m+1) where m is aninteger from 1 to
 6. 4. The process of claim 1 wherein the promoter isselected from the group consisting of aliphatic heterocyclic compoundswhich contain at least one carbon-nitrogen double bond in the,heterocyclic ring.
 5. The process of claim 4 wherein the halogenatedalkane is selected from the group consisting of CBrCl₃, CBrF₃, CCl₄,CCl₃ F, CCl₂ F₂, CF₃ I, CCl₂ FCCl₂ F, CCl₃ CF₃, CCl₃ CF₂ CF₃, CCl₃ CH₂CCl₃, CF₃ CF₂ I, CF₃ CF₂ CF₂ I, CCl₃ CH₂ CF₃, and CCl₃ (CF₂ CF₂)_(q) Clwhere q is an integer from 1 to
 6. 6. The process of claim 5 wherein theolefin is selected from the group consisting of CF₂ ═CF₂, CF₂ ═CClF, CF₂═CCl₂, CClF═CClF, CClF═CCl₂, CF₂ ═CHF, CF₂ ═CH₂, CHF═CHF, CHF═CH₂, CH₂═CH₂, CH₂ ═CHCH₃, CH₂ ═CHCF₃, CH₂ ═CFCF₃, CH₂ ═CHCl, CH₂ ═CCl₂,CHCl═CHCl, CHCl═CCl₂, CH₂ ═CHCl, CH₂ ═CHCH₂ Cl, CH₂ ═CHAryl, CH₂ ═CHCO₂CH₃, CH₂ ═C(CH₃)CO₂ CH₃, CH₂ ═CHCO₂ C₂ H₅, and CH₂ ═C(CH₃) CO₂ C₂ H₅. 7.The process of claim 4 wherein the copper catalyst is selected from thegroup consisting of copper(I) chloride, copper(II) chloride, copper(I)bromide, copper(II) bromide, copper(I) iodide, copper(II)acetate andcopper(II) sulfate.
 8. The process of claim 4 where the reaction is donein the presence of a solvent selected from the group consisting ofacetonitrile, dimethyl sulfoxide, dimethyl formamide, tetrahydrofuran,isopropanol, t-butanol, polyethers of the formula R⁹ O(CH₂ CH₂ O)_(r) R⁹where each R⁹ is independently selected from the group consisting of H,CH₃ and C₂ H₅ and r is an integer from 1 to 4, esters of the formula R¹⁰CO₂ R¹⁰ where each R¹⁰ is independently selected from C₁ -C₆ alkylgroups and mixtures thereof.
 9. The process of claim 8 wherein thesolvent is acetonitrile.
 10. The process of claim 4 wherein the reactionis accomplished in a homogenous system.
 11. The process of claim 4wherein the promoter is selected from the group consisting ofimidazoles, imidazolines, oxadiazoles, oxazoles, oxazolines, isoxazoles,thiazoles, thiazolines, pyrrolines, trihydropyrimidines, pyrazoles,triazoles, triazolium salts, isothiazoles, tetrazoles, tetrazoliumsalts, thiadiazoles, oxazines and dihydrooxazine.
 12. The process ofclaim 1 wherein the halogenated alkane is selected from the groupconsisting of CBrCl₃, CBrF₃, CCl₄, CCl₃ F, CCl₂ F₂, CF₃ I, CCl₂ FCCl₂ F,CCl₃ CF₃, CCl₃ CF₂ CF₃, CCl₃ CH₂ CCl₃, CF₃ CF₂ I, CF₃ CF₂ CF₂ I, CCl₃CH₂ CF₃, and CCl₃ (CF₂ CF₂)_(q) Cl where q is an integer from 1 to 6.13. The process of claim 12 wherein the olefin is selected from thegroup consisting of CF₂ ═CF₂, CF₂ ═CClF, CF₂ ═CCl₂, CClF═CClF,CClF═CCl₂, CF₂ ═CHF, CF₂ ═CH₂, CHF═CHF, CHF═CH₂, CH₂ ═CH₂, CH₂ ═CHCH₃,CH₂ ═CHCF₃, CH₂ ═CFCF₃, CH₂ ═CHCl, CH₂ ═CCl₂, CHCl═CHCl, CHCl═CCl₂, CH₂═CHCl, CH₂ ═CHCH₂ Cl, CH₂ ═CHAryl, CH₂ ═CHCO₂ CH₃, CH₂ ═C(CH₃)CO₂ CH₃,CH₂ ═CHCO₂ C₂ H₅, and CH₂ ═C(CH₃) CO₂ C₂ H₅.
 14. The process of claim 1wherein the copper catalyst is selected from the group consisting ofcopper(I) chloride, copper(II) chloride, copper(I) bromide, copper(II)bromide, copper(I) iodide, copper(II) acetate and copper(II) sulfate.15. The process of claim 3 wherein the promoter is a promoter of FormulaII which is optically active.
 16. The process of claim 1 where thereaction is done in the presence of a solvent selected from the groupconsisting of acetonitrile, dimethyl sulfoxide, dimethyl formamide,tetrahydrofuran, isopropanol, t-butanol, polyethers of the formula R⁹O(CH₂ CH₂ O)_(r) R⁹ where each R⁹ is independently selected from thegroup consisting of H, CH₃ and C₂ H₅ and r is an integer from 1 to 4,esters of the formula R¹⁰ CO₂ R¹⁰ where each R¹⁰ is independentlyselected from C₁ -C₆ alkyl groups and mixtures thereof.
 17. The processof claim 16 wherein the solvent is acetonitrile.
 18. The process ofclaim 1 wherein the reaction is accomplished in a homogenous system. 19.A process for producing a hydrofluoroalkane comprising:(a) producing ahydrochlorofluoroalkane by reacting AB and CR¹ R² ═CR³ R⁴ in accordancewith the process of claim 1, provided that B and X are Cl and at leastone of AB and CR¹ R² ═CR³ R⁴ contain hydrogen; and (b) reacting thehydrochlorofluoroalkane produced in (a) with HF.